Quantum Field Theory on Spacetimes with a Compactly Generated Cauchy Horizon

We prove two theorems which concern difficulties in the formulation of the quantum theory of a linear scalar field on a spacetime, , with a compactly generated Cauchy horizon. These theorems demonstrate the breakdown of the theory at certain base points of the Cauchy horizon, which are defined as ‘past terminal accumulation points’ of the horizon generators. Thus, the theorems may be interpreted as giving support to Hawking's ‘Chronology Protection Conjecture’, according to which the laws of physics prevent one from manufacturing a ’time machine‘. Specifically, we prove: Theorem 1. There is no extension to of the usual field algebra on the initial globally hyperbolic region which satisfies the condition of F-locality at any base point. In other words, any extension of the field algebra must, in any globally hyperbolic neighbourhood of any base point, differ from the algebra one would define on that neighbourhood according to the rules for globally hyperbolic spacetimes. Theorem 2. The two-point distribution for any Hadamard state defined on the initial globally hyperbolic region must (when extended to a distributional bisolution of the covariant Klein-Gordon equation on the full spacetime) be singular at every base point x in the sense that the difference between this two point distribution and a local Hadamard distribution cannot be given by a bounded function in any neighbourhood (in M × M) of (x,x). In consequence of Theorem 2, quantities such as the renormalized expectation value of φ² or of the stress-energy tensor are necessarily ill-defined or singular at any base point. The proof of these theorems relies on the ‘Propagation of Singularities’ theorems of Duistermaat and H?rmander. Received: 14 March 1996/Accepted: 11 June 1996     

Photoexcited state properties of H2-porphyrin/C60-based rotaxanes as studied by time-resolved electron paramagnetic resonance spectroscopy

Light-driven intramolecular electron transfer (ET) and energy transfer (EnT) processes in two rotaxanes, the first containing two free base porphyrins and C(60) fullerene moieties incorporated around a Cu(I)bisphenanthroline core ((H(2)P)(2)-Cu(I)(phen)(2)-C(60)) and a second lacking the fullerene moiety ((H(2)P)(2)-Cu(I)(phen)(2)), were studied by X-band (9.5 GHz) time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The experiments were performed in frozen toluene and ethanol and different phases of the nematic liquid crystal (E-7). It is demonstrated that the ET and EnT processes in the (H(2)P)(2)-Cu(I)(phen)(2)-C(60) rotaxane in different media result in the formation of the same charge-separated state, namely (H(2)P)(2)(?+)-Cu(I)(phen)(2)(?-)-C(60), while photoexcitation of the (H(2)P)(2)-Cu(I)(phen)(2) rotaxane does not induce noticeable transfer processes in these matrices. The results are discussed in terms of the high conformational mobility of the rotaxanes, which enables changes in the molecular topography and resultant modification of the rates and routes of photoinduced processes occurring in these systems. The parameters of the transfer processes are compared with those obtained in our previous study of (ZnP)(2)-Cu(I)(phen)(2)-C(60) and (ZnP)(2)-Cu(I)(phen)(2) rotaxanes under the same experimental conditions.     

Crystallization kinetics and excess free energy of H2O and D2O nanoscale films of amorphous solid water

Temperature-programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS) are used to investigate the crystallization kinetics and measure the excess free energy of metastable amorphous solid water films (ASW) of H(2)O and D(2)O grown using molecular beams. The desorption rates from the amorphous and crystalline phases of ASW are distinct, and as such, crystallization manifests can be observed in the TPD spectrum. The crystallization kinetics were studied by varying the TPD heating rate from 0.001 to 3 K/s. A coupled desorption-crystallization kinetic model accurately simulates the desorption spectra and accurately predicts the observed temperature shifts in the crystallization. Isothermal crystallization studies using RAIRS are in agreement with the TPD results. Furthermore, highly sensitive measurements of the desorption rates were used to determine the excess free energy of ASW near 150 K. The excess entropy obtained from these data is consistent with there being a thermodynamic continuity between ASW and supercooled liquid water.     

A gram scale synthesis of a multi-13C-labelled anthocyanin, [6,8,10,3',5'-13C5]cyanidin-3-glucoside, for use in oral tracer studies in humans

The major dietary anthocyanin, cyanidin-3-glucoside, was prepared on a 4 g scale from three units of diethyl [2-(13)C]malonate and one unit of [1,3-(13)C(2)]acetone, such that five isotope locations were distributed throughout the molecule to provide a penta-(13)C(5)-labelled anthocyanin, [6,8,10,3',5'-(13)C(5)]cyanidin-3-glucoside chloride, for use in human stable-isotope tracer studies.     

Determining valine side-chain rotamer conformations in proteins from methyl 13C chemical shifts: application to the 360 kDa half-proteasome

A method is presented for determining Val side-chain χ(1) rotamer distributions in proteins based exclusively on measured (13)C(γ1) and (13)C(γ2) chemical shifts. The approach selects an ensemble of 20 χ(1) values, calculates average methyl (13)C(γ1,γ2) chemical shifts via theoretical quantum chemical calculations and maximizes the agreement with the experimentally measured shifts using a genetic algorithm. The methodology is validated with an application involving six proteins for which (13)C(γ) chemical shifts and three-bond methyl-backbone scalar couplings are available. The utility of the methodology is demonstrated with an application to the 360 kDa 'half-proteasome' where the χ(1) rotameric distributions of Val residues are calculated on the basis of chemical shifts. For the most part the χ(1) profiles so obtained compare very well with those generated from the high-resolution (2.3 ?) X-ray structure of the proteasome. Both NMR and X-ray distributions are cross-validated by comparing calculated (1)H-(13)C methyl residual dipolar couplings with measured values, and the level of agreement is at least as good for the NMR derived χ(1) values. Notably, as the resolution of the X-ray data improves (rotamer distributions from 3.4 and 2.3 ? X-ray structures are compared with the NMR data), the agreement with the NMR gets significantly better. This emphasizes the importance of NMR approaches for the study of high molecular weight complexes that can be recalcitrant to high resolution X-ray analysis.     

Communication: direct angle-resolved measurements of collision dynamics with electronically excited molecules: NO(A2Σ+) + Ar

We report direct doubly differential (quantum state and angle-resolved) scattering measurements involving short-lived electronically excited molecules using crossed molecular beams. In our experiment, supersonic beams of nitric oxide and argon atoms collide at 90°. In the crossing region, NO molecules are excited to the A(2)Σ(+)state by a pulsed nanosecond laser, undergo rotationally inelastic collisions with Ar atoms, and are then detected 400 ns later (approximately twice the radiative lifetime of the A(2)Σ(+)state) by 1 + 1(') multiphoton ionization via the E(2)Σ(+) state. The velocity distributions of the scattered molecules are recorded using velocity-mapped ion imaging. The resulting images provide a direct measurement of the state-to-state differential scattering cross sections. These results demonstrate that sufficient scattering events occur during the short lifetimes typical of molecular excited states (～200 ns, in this case) to allow spectroscopically detected quantum-state-resolved measurements of products of excited-state collisions.